Permanent press fabric resin from crotonylidenediurea-glyoxal-formaldehyde aminoplast material

ABSTRACT

Crotonylidenediurea is reacted with glyoxal and the resulting adduct methylolated with formaldehyde to produce the corresponding trimethylolated derivative which exhibits very desirable properties as a permanent press resin for fabrics.

United States Patent Powanda et al.

Sept. 2, 1975 PERMANENT PRESS FABRIC RESIN FROM CROTONYLIDENEDIUREA-GLYOXAL- FORMALDEHYDE AMINOPLAST MATERIAL lnventors: Thomas M. Powanda. Middlesex:

Lawrence B. Holzman. West Orange; James E. Tracy. Somerset.

Appl. No.: 381,1 I6

Related U.S. Application Data Division of Ser. No. 135.781. April 20. 197l. Pat. No. 3.764.263.

U.S. CI..... 260/67.7; 260/676 R; 260/2564 C;

260/2564 F Int. Cl C08g 9/26 Field of Search 260/675. 67.6 R. 67.7,

References Cited UNITED STATES PATENTS 4 1940 12/1941 6/1965 7/l967 9/l969 l2/l969 1/1971 Widmer ct al. 260/676 Ott et al 260/69 UX Brandeis et al. 7 l/l l X Mills 106/165 Ungar 260/67.6

Deuzeman 260/677 Standish et al. 260/677 X Primary E.\'un1in0r-Howard E. Schain Aim/nay. Agent. or Firn1Th0mas J. Morgan. Esq.; John A. Shedden. Esq.

ABSTRACT Crotonylidenediurea is reacted with glyoxal and the resulting adduct methylolated with formaldehyde to produce the corresponding trimethylolated derivative which exhibits very desirable properties as a permanent press resin for fabrics.

2 Claims. No Drawings 1 PERMANENT PRESS FABRIC RESIN FROM CROTONYLIDENEDIUREA-GLYOXAL- FORMALDEHYDE AMINOPLAST MATERIAL This is a division of application Ser. No. 153,781, filed Apr. 20, 1971, now US. Pat. No. 3,764,263.

BACKGROUND OF THE INVENTION In the last decade permanent press" fabrics have been a real boon to the textile industry. The future looks even brighter as consumers look for permanent press properties in other than casual wear, shirts and like apparel. It is anticipated, for instance, that use of permanent press resins in household white goods. e.g., sheets, pillowcases and tablecloths. will account for a substantial amount of the increased demand in this decade. To meet this demand the resins must be able to impart permanent press properties without degrading the fiber from which the fabric is made. Typically, the fabric is made of cellulosic materials, e.g.. cotton, cotton-polyester blends, regenerated cellulosic materials, such as rayon, etc. Degradation can occur, for example, when the resin finish is applied and cured; it may also occur as a result of repeated washings of the treated fabric using the various popular bleaehes and detergents.

The concept of permanent press is twofold: crease resistance" and crease retention. Crease resistance is synonymous with wrinkle. resistance and wrinkle recovery", viz., the ability of a treated fabric to resist wrinkling and to retain smoothness of shape and hand upon repeated wear and laundering. Crease retention is synonymous with durable press, viz., the ability of a treated fabric to drip-dry without loss of crease and to be worn without ironing.

Obviously, achievement of all of these desirable properties, and others such as resistance to soil redeposition, and the like, requires chemicals which are quite special. The objects of the present invention, therefore, are to produce and provide just such special chemical compositions which, when applied to fabrics as taught herein, impart these very desirable properties.

THE INVENTION According to the instant discovery, novel chemical compositions have been found from which resins are readily prepared, the latter exhibiting, as will be seen hereinafter, permanent press characteristics of the type intensely sought after by the textile industry and hereinbefore briefly described. The novel compounds of the present invention are prepared from crotonylidenediurea (A), also referred to herein as CDU, by reacting LII (A) I with glyoxal to form a 1,2hdyroxyethy1- substituted crotonylidenediurea adduct (B) which is methylolatcd with formaldehyde to produce the corresponding trimethylolatcd derivative (C), the latter being used to treat fabrics, pursuant to the present invention. to impart thereto significant permanent press characteristics.

Reaetant (A). above, viz., crotonylidenediurea. may be prepared by reacting urea with acetaldehyde in an acidic hydroxylic medium, e.g., as described in US. Pat. No. 3.190.741. While it has been found that crotonylidenediurea suitable for use in the present invention' is conveniently and preferably prepared according to the following procedure, it should be understood that other methods of synthesis can be used: Thus, 270 parts of urea, parts and percentages used herein being by weight unless otherwise indicated, is added to a mixture of 99 parts of acetaldehyde and 600 parts of distilled water in a suitable conventional reaction vessel. The resultant solution is heated to a temperature of about C. Thirty parts of phosphoric acid (catalyst) is then added and the temperature is thereafter maintained at between about 60C and about C for 1 hour during which time product crystallizes and settles out. The reaction mixture is subsequently cooled to ambient temperature whereupon further crystalline product crotonylidenediurea settles out. The product is separated from the supernatant liquid by filtration, washed with water. and dried in vacuo. The yield of white, solid crotonylidenediurea (135.3 grams) is 69.9

percent of thetheoretical, based on the weight of acetaldehyde. Elemental analysis of the product corresponds to the formula C I-I O- N, and the infrared spectrum thereof (Nujol mull) is identical to that reported in the literature (cf. Japanese Letters Patent No. 492,348) for crotonylidenediurea.

In accordance with the instant discovery, CDU readily reacts with glyoxal as follows:

EQUATION I (A) CDU and (B) CDU-Glyoxal Adduct EQUATION ll cooled and pH adjusted to about neutral. Broadly, a temperature above about 40C to about 105C is contemplated herein, the upper temperature being, preferably, no greater than about atmospheric reflux temper- CDU-(llyoxal Adduct ."lHCHO ll H(|) (|)H C H(-(H HOH. -N N-cH oH and I I O H(\ CH 2, u u HC 0 (.H C H;,C C N NCH. ,OH

(.H OH 1 H;.( C N N H H HC CH l l I H H (.HJOH L H. ,()H HO OH (C) (DU-(llyoxul-HCHO The exact nature of adduet (B) in Equation 1, above, ature. is not known but it is believed to be a mixture as shown As in the case of the Equation l reaction described in the equation: likewi trim hylolation f the interhereinbefore, reaction conditions for the Equation II mediate (B) of'Equation 1 yields what is believed to be the CDU/Glyoxal/HCHO mixture (C) illustrated in Equation ll.

lntermediate (B) is best prepared by reacting equimolar proportions of glyoxal and CDU in a hydroxylic mediu'm, preferably water, at elevated temperatures and atmospheric pressure. Preferably, reaction is carried out for the most part at relatively low temperatures, e.g., in the range of about 40C to about 75C, and then the reaction is completed by increasing the temperature to atmospheric reflux for a relatively short period of time. Usually it is best to maintain the lower temperature for less than about an hour and then bring the reaction mixture to reflux for about 3 to about 15 minutes. Of course, these temperatures may be varied considerably, depending upon concentrations of reactants, medium used, and other like factors. It should be understood that, in view of the fact that the reaction proceeds rather readily, a wide variety of temperatures, concentrations and pressures is permissible, the reaction conditions just mentioned being those best suited for equimolar proportions of reactants. Obviously, pressures above or below atmospheric require higher or lower temperatures, respectively; obviously, also, lean or excess concentrations, below or above stoichiometric, affect the temperature requirements for optimum results. In short, the reaction conditions are quite flexible, the stringencies being imposed by desired efficiencies.

Conversion of intermediate (B) to the CDU-Glyoxal- HCHO composition (C) of Equation II, above, likewise admits of a wide variety of reaction conditions. Reaction is best carried out in a hydroxylic medium, usually water. Generally, between about 2.80 and about 5.0 molar proportions of formaldehyde, preferably between about 2.90 and about 3.05, is used based on adduet (B). Typical desirable formaldehyde sources are formalin, paraformaldehyde, and the like.

Admixture of adduet (B) with, say, an aqueous solution of formaldehyde gives rise to an exotherm. When the exotherm subsides (about 40C), the mixture of reactants if preferably heated for up to several hours,

reaction are very flexible, the stringencies also generally being dictated by desired efficiencies. If pressures above or below atmospheric are used, proportionately higher or lower temperatures, respectively, are usually indicated; likewise, lean or excess concentrations of formaldehyde with respect to adduct- (B) could affect the temperature requirements for optimum results, as would, of course, the amount of water or other hydroxylic medium used relative to the reactants.

Fabric treatment is carried out in a conventional pad bath in an aqueous medium containing the resinforming compound (C), viz., the CDU-Glyoxal-HCl-IO composition derived from adduet (B), and a curing catalyst as the principal ingredients. Generally, small amounts of surfactant and softener are present to enhance transfer of compound (C) to the fabric being treated.

The catalyst functions to catalyze the curing process which takes between about 5 seconds and about 30 minutes, preferably between about 3 minutes and about 15 minutes, at temperatures in the range of about 275F to about 425F, preferably between about 300F and about 350F. Substances suitable for catalysing the curing process include any conventional acidic catalysts or like catalysts heretofore known to be useful in catalysing the curing of conventional aminoplast materials. Such acid catalysts are employed in conventional amounts, e.g., at a concentration of between about 1 percent and about 50 percent by weight, based on the weight of aminoplast material. Typical catalysts contemplated herein are the water-soluble inorganic salts which behave as so-called latent acid catalysts, e.g., ammonium chloride, magnesium chloride, zinc nitrate, and the like.

According to a preferred mode of carrying out the fabric treatment process of the present invention, the aqueous reaction mixture containing novel compound (C) dissolved therein is cooled to ambient temperature, brought to a pH of about 7.0, and filtered to remove any insolubles which may be present. Then it is diluted with water to the desired concentration, mixed with a conventional amount of an acidic curing catalyst, and the fabric to be treated is immersed therein. The amount of resin pickup" by the substrate fabric is determined in large measure by the concentration of the resin-forming material, viz., compound (C), in the aqueous pad bath solution. Generally. the concentration of compound (C) in the pad bath solution (which can be determined gravimetrically) ranges between about 2 percent or less and about 65 percent by weight or more, for cellulosic fabrics. Preferably, a pad bath concentration of between about 5 percent and-about 45 percent is used, with a concentration of between l0 percent and about percent being especially preferred. Percentages are based upon the total weight of the pad bath solution. The particular desired concentration of resin-forming substance in any given instance can be conveniently achieved by appropriate adjustment of the concentrations of reactants (i.e., CDU/- glyoxal/I-ICHO) or by the judicious addition of water to an initially relatively highly concentrated solution of resin-forming compound (C).

After saturating the fabric with the pad bath solution, the treated fabric is withdrawn from the bath, wrung between rollers made of an inert material (e.g., metal, ceramic, rubber, and the like), preferably rubber rollers or adjacent, cooperatively-functioning stainless steel/rubber rollers, dried and simultaneously or subsequently heat cured at a temperature within the aforementioned range. The heat curing step can, if desired, be conducted by contacting the fabric with heated metal rollers, preferably heated stainless steel rollers.

In the present invention, the percent pickup of the CDU/Glyoxal/I-ICHO composition is measured as: 7( Wet Pickup, after immersion in the pad bath solution; Dry Pickup, after curing; 7: Dry Pickup, after I wash; and Dry Pickup, after 21 washes.

As will be seen hereinafter, all tests are comparative tests using commercial resins as controls and comparing these resins with the novel composition (C) of the instant discovery. The tests recorded herein, other than resin pickup characteristics, are intended to illustrate the effectiveness of compound (C) with respect to wrinkle recovery, hand, deterioration of fabric, soil redeposition, and the like. Obviously, permanent press.

resins are not attractive if they deleteriously affect fiber strength, if wrinkle recovery is poor, etc.

Fabrics, particularly cellulosic fabrics, treated with compound (C) according to the present invention exhibit, as will be seen hereinafter, very desirable and valuable permanent press properties. The examples which follow teach the novel CDU-Glyoxal adduct (B) and the novel CDU/Glyoxal/HCI-IO composition (C) of the instant discovery and processes for preparing same. In addition, treatment of fabrics with resin-forming compound (C) is fully disclosed, as well as anumber of tests comparing the latters efficacy with that of the following commercially popular resin-forr'ning compounds:

0 ll HOH C C CH- ,OH O

\ 0 g N Cmon N' N R L l l CH- -OH HC CH [R hydroxyalkyl or alkyl] HO OH PERMAFRESH*I 13B AEROTEX**82 (dimethyloldihydroxyethyleneurea) (carbamatc) DMDHEU Trademark for permanent press compound sold by Sun ('hemieal (o., Wood River Junction. R.l.

"Trademark for permanent press compound sold by American ('yanainid Co., Bound Brook, NJ.

The following examples are merely intended to be illustrative of certain of the preferred embodiments within the spirit and scope of the present invention and, therefore, are not to be interpreted too restrictively; parts and percentages given in the examples are by weight, unless otherwise indicated:

EXAMPLE I To a reaction vessel is fed 468 grams of crotonylidenediurea, 395 grams of 40% glyoxal aqueous solution and water, thus providing a CDU/Glyoxal molar ratio of 1:1. Sufficient water is introduced to obtain good stirring (approximately grams). The mixture of reactants is heated to 60C, held at that temperature for 45 minutes, and then slowly heated to atmospheric reflux 103C). and held at that temperature for 5 minutes before cooling the reaction mixture to ambient temperature and, then filtering to remove unreacted CDU 128 grams). The filtrate 1055 grams) therefore contains 340 grams (approximately 2 moles) of reacted CDU, i.e., the CDU/Glyoxal adduct (B), described hercinabove in Equation I, in solution.

EXAMPLE II TABLE I "A" I /r free Compound Solids pH HCHO Aerotex 82 I I 48i2* 6.5 3.2 Permafresh 113B 45:? 5,9 0 CDU/Glyoxal/HCHO 39 7.0 l

*Published values EXAMPLE III The product CDU/Glyoxal/HCI-IOcomposition (C) of Example II, above, is used to treat'plain weave white 50/50 cotton-polyester (PE) cloth, of the type used in shirts or household goods (e.g., sheets" and pillowcases). The tests procedure is as follows:

Bath: Compound tested 7:

(dry weight basis) l0.0 Surfactant (Triton*X I00) 0.2 Softener (I.ubritron**KN) 3.0 Catalyst KR(MgCl solution)*** 5.0 Water 8 l .8

-Continued Conventional soil redeposition tests showed the Pmccdure a product of Example 11. i.e., compound (C), to be supe- Dry zzu p for zlminmcs rior to Pcrmafresh 1 13B (DMDHEU). Using a small grifffkt lcr 12 in amount of anti-soil-rede position agent for polyester/- Afler wa-sh 5 cotton blends when sub ecting the fabric of Example l-tl1ulr ICSIISWUICIICS are laundered IIl. treated as taught in the same Example, to an other SIS: i l wise conventional soil redeposition test showed the fabslmtncss ric treated with CDU/Glyoxal/HCHO compound (C) (ASTM D I 7; (4T performed as well as the Aerotex 82 treated fabric and Triton X-l00 is zi trudcmar k ftir a n nlkyluryl poly ether :ilcuhifl surfactant sold 10 better than )ermafresh l IBB-treated fabric under by Ruhm & Haas 0. Philadel hia. Pu. the same conditions. In other words, the Aerotex 82- I;311111172;iii-825.?fhlhiti iiffittiilcfi$7?"" tteeted we end the eemeeund tfeeeie g t i c ls ju g l gllx :hatrium-leased c;ll.ll \s\ solution sold h Sun both remained almost completely white. The anti-soilredeposition agent used is a water-soluble methyl cellu- The following table shows the pickup properties of lose derivative (4000 cps) bearing the trademark ME- each of the. controls as compared with compound (C), THOCEL-90-HG and sold by Dow Chemical Corp.,

the product of Example II, above: Midland, Michigan. A concentration of 1%, by weight,

TABLE II I RESIN ADD()N 7! Wet /r Dry 7: Dry 7: Dry Pickup Pickup Pickup Pickup (after I wash) (after 21 washes) Aerotex 82 78 7.0 5.4 Permafresh 113B 78 24.7 6.5 CDU/Glyoxal/HCHO 77.7 8.9 1.6

Wrinkle recovery characteristics of the fabric of Exof Methocel-l-IG is added to the conventional soil redeample Ill, above, treated with the compounds of Table position test soiling bath alluded to hereinabove; the II is determined by a well-known method: ASTM D- concentration, viz., 1% by weight, is based on the total l295-67-Warp direction only. The results of these tests 0 weight of the soil bath. The use of methyl cellulose defollow: rivatives (Methocel) is claimed in copending applica- TABLE Ill WRINKLE RECOVERY Recovery in Degrees Cantilever stiffness of the fabric of Example III using tion Ser. No. 22,140 filed Apr. 2, l970, by A. S. Forthe compounds of Table II is determined using the schirm-et al. and entitled Anti-soiling Polyester Textile method: ASTM D-1388-64-Warp direction only. The Material, 110W results are as follows: As is evident from Tables Ill and IV, above, the wrin- TABLE IV CANTlLEVER STIFFNESS Flexural Rigidity (mg-cm.)

After 20 Initial Wash Cycles Blank (Untreated /50 PEzCotmn 79.95 67.58 Aerotex 8'. 88.68 62.l7 CONTROLS Permafresh l 138 89.43 55.94 CDU/Glyoxal/HCHO 65.25 60.73

Tearing strength of the fabric of Example III, above, kle recovery and stiffness performance of compound using the compounds of Table II is determined by the (C) compares very favorably with the performance of method: ASTM D-226l-64T-Warp direction only. The the commercial resins, even after multiple launderings. results are as follows: This indicates, in the case of wrinkle recovery, good TABLE V TEARING STRENGTH BY THE TONGUE (SINGLE RIP) METHOD Break Load (in pounds) 9 bonding of the compound (C) resin to the fabric. Tear strength data reported in Table V. above. showed com- 10 l. A trimethylolatcd CDU/Glyoxal/HCHO derivative of the formulae (C):

pound (C). like the commercial controls. produced no significant deterioration in fiber strength. Abrasion resistance tests (ASTM D-l l75-64T) not tabulated hcreinabove, likewise indicated no significant deterioration in fiber strength.

Pursuant to statutory requirements, there are described above the invention and what are now considered its best embodiments. It should be understood. however, that the invention can be practiced otherwise than as specifically described, within the scope of the appended claims.

What is claimed is:

2. A method for the preparation of an aminoplast material comprising 

2. A METHOD FOR THE PREPARATION OF AN AMINOPLAST MATERIAL COMPRISING REACTING CROTONYLIDENEDIUREA WITH AN ABOUT EQUIMOLAR PROPORTION OF GLYOXAL IN A HYDROXYLIC MEDIUM AT AN ELEVATED TEMPERATURE OF FROM ABOUT 40*C TO ABOUT ATMOSPHERIC REFLUX TO FORM A 1, 2-HYDROXYETHYL-SUBSTITUTED CROTONYLIDENEDIUREA ADDUCT, AND REACTING SAID ADDUCT WITH BETWEEN ABOUT 2.80 AND ABOUT 5.0 MOLAR PROPORTIONS OF FORMALDEHYDE IN A HYDROXYLIC MEDIUM AT AN ELEVATED TEMPERATURE OF FROM ABOUT 40*C TO ABOUT ATMOSPHERIC REFLUX, AND RECOVERING AN AMINOPLAST MATERIAL.
 2. A method for the preparation of an aminoplast material comprising reacting crotonylidenediurea with an about equimolar proportion of glyoxal in a hydroxylic medium at an elevated temperature of from about about 40*C to about atmospheric reflux to form a 1, 2-hydroxyethyl-substituted crotonylidenediurea adduct; and reacting said adduct with between about 2.80 and about 5.0 molar proportions of formaldehyde in a hydroxylic medium at an elevated temperature of from about 40*C to about atmospheric reflux; and recovering an aminoplast material. 